JP2001239164A - Cadmium sulfide-based photocatalyst for hydrogen generation, its manufacturing method, and method for manufacturing hydrogen using the photocatalyst - Google Patents
Cadmium sulfide-based photocatalyst for hydrogen generation, its manufacturing method, and method for manufacturing hydrogen using the photocatalystInfo
- Publication number
- JP2001239164A JP2001239164A JP2000057978A JP2000057978A JP2001239164A JP 2001239164 A JP2001239164 A JP 2001239164A JP 2000057978 A JP2000057978 A JP 2000057978A JP 2000057978 A JP2000057978 A JP 2000057978A JP 2001239164 A JP2001239164 A JP 2001239164A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- cadmium sulfide
- cds
- hydrogen
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910003953 H3PO2 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims 1
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 claims 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000012298 atmosphere Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規の水素発生用光
触媒及びその製造方法とそれを用いる水素の製造方法に
関するもので，より詳しくは，光反応による水からの水
素の製造に使用される新規の硫化カドミウム（ＣｄＳ）
系光触媒及びその製造方法とそれを用いる水素の製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydrogen generating photocatalyst, a method for producing the same, and a method for producing hydrogen using the same. More specifically, the present invention relates to a novel photocatalyst used for producing hydrogen from water by a photoreaction. Cadmium sulfide (CdS)
The present invention relates to a photocatalyst, a method for producing the same, and a method for producing hydrogen using the same.
【０００２】[0002]
【従来の技術】水素はアンモニア，メタノールなどの製
造原料として使用され，飽和化合物を生成させる水素化
反応の必須原料である。同時に，水素添加反応，脱硫反
応，脱窒素反応，脱金属反応などのような水素処理工程
に使用されており，特に，最近の地球温暖化の主原因と
して注目を浴びている二酸化炭素の固定化反応に必ず使
用されている。また，水素は清浄な代替エネルギーの一
つで，現在の化石原料に代わる未来のエネルギー源とし
て大きく期待されている。2. Description of the Related Art Hydrogen is used as a raw material for producing ammonia, methanol and the like, and is an essential raw material for a hydrogenation reaction for producing a saturated compound. At the same time, it is used in hydrotreating processes such as hydrogenation, desulfurization, denitrification, and demetallation, and in particular, the fixation of carbon dioxide, which has recently attracted attention as a major cause of global warming. Always used for reactions. Hydrogen is one of the clean alternative energy sources, and is expected as a future energy source to replace the current fossil raw material.
【０００３】水素を製造する方法として従来用いられて
来たものには、ナフサ及び天然ガスのような化石燃料を
改質して水素を製造する方法，高温で鉄と水蒸気を接触
させる方法，アルカリ金属と水を反応させる方法，及び
水の電気分解などが挙げられる。[0003] Conventional methods for producing hydrogen include a method of producing hydrogen by reforming fossil fuels such as naphtha and natural gas, a method of contacting iron with steam at high temperatures, and a method of producing hydrogen. Examples include a method of reacting a metal with water, and electrolysis of water.
【０００４】しかし，これらの方法は根本的に多くのエ
ネルギーを必要とするため，決して経済的ではない。化
石燃料の改質の場合は，は多量の二酸化炭素を副生させ
る問題があり，また，水の電気分解の場合は，電極の寿
命と，副生する酸素の処理という問題が常に存在する。
このような根本的な問題のため，実際の水素製造設備に
は高い費用がかかっていた。[0004] However, these methods are not economical at all because they basically require a lot of energy. In the case of fossil fuel reforming, there is a problem that a large amount of carbon dioxide is produced as a by-product, and in the case of electrolysis of water, there are always problems of the life of the electrode and the treatment of by-product oxygen.
Because of these fundamental problems, actual hydrogen production facilities were expensive.
【０００５】一方，自然界での水素はたいてい水の形態
で存在し，また，そのほかの無機化合物として存在して
いる。気体状態の水素は，比重が小さいため，大気中に
存在する量は非常に少ない。On the other hand, hydrogen in nature exists mostly in the form of water, and also exists as other inorganic compounds. Since gaseous hydrogen has a low specific gravity, the amount present in the atmosphere is very small.
【０００６】また，無機化合物の形態として存在する水
素は，純粋に分離することが技術的に難しいだけでな
く，分離過程に高い費用がかかるので経済性がなく実際
的でない。したがって，水から水素を効率的に製造する
技術は非常に意味がある課題であった。In addition, hydrogen present in the form of an inorganic compound is not only technically difficult to separate purely, but also involves a high cost in the separation process, which is not economical and impractical. Therefore, the technology for efficiently producing hydrogen from water has been a very significant issue.
【０００７】水から水素を効率的に製造する技術には，
近年注目されているものとして光触媒を用いる水の分解
技術が挙げられる。水素製造用光触媒に関する先行技術
はその数はまだ少なく，日本国特開昭６２−１９１０４
５号，同６３−１０７８１５号，そして本発明者による
下記の出願がある。[0007] Technologies for efficiently producing hydrogen from water include:
In recent years, a technique of decomposing water using a photocatalyst has been attracting attention. The prior art relating to photocatalysts for hydrogen production is still few in number.
No. 5, 63-107815, and the following application filed by the present inventors.
【０００８】前記日本国特開昭６２−１９０４５号は，
希土類元素化合物を光触媒として使用し，Ｎａ２Ｓ水溶
液の光分解反応により水素を発生させることを特徴と
し，可視光線に光触媒が活性を呈する利点がある。前記
日本国特開昭６３−１０７８１５号は，ニオブとアルカ
リ土類金属の複合酸化物を光触媒として使用し，メタノ
ール水溶液の光分解反応により水素を発生させることを
特徴とし，これもやはり可視光線に触媒が活性を示す利
点がある。しかしながら，前記両技術による水素製造方
法は，水素生成量において，その発生量が１０ｍｌ／
０．５ｇｈｒ程度と非常に少ないという問題があった。The Japanese Patent Application Laid-Open No. 62-19045 discloses that
It is characterized in that a rare earth element compound is used as a photocatalyst and hydrogen is generated by a photolysis reaction of an aqueous Na 2 S solution, and there is an advantage that the photocatalyst exhibits activity in visible light. Japanese Patent Application Laid-Open No. 63-107815 is characterized in that a composite oxide of niobium and an alkaline earth metal is used as a photocatalyst and hydrogen is generated by a photolysis reaction of an aqueous methanol solution, which is also converted to visible light. There is the advantage that the catalyst shows activity. However, in the hydrogen production method according to the two technologies, the amount of generated hydrogen is 10 ml /
There was a problem that the amount was as small as about 0.5 ghr.
【０００９】前記のような問題点を解決するためのもの
として，本発明者による韓国特許出願第９５−７７２１
号，同９５−３０４１６号，同９６−４４２１４号が挙
げられる。前記韓国特許出願第９５−７７２１号の技術
は，下記の化学式２で表示される光触媒を使用し，ホル
ムアルデヒド，アルコールなどの含酸素有機物促進剤が
混合された水溶液に紫外光を照射して水素を発生させる
ことを特徴とする。In order to solve the above problems, Korean Patent Application No. 95-7721 filed by the present inventor has been proposed.
Nos. 95-30416 and 96-44214. The technology disclosed in Korean Patent Application No. 95-7721 uses a photocatalyst represented by the following Chemical Formula 2 to irradiate an aqueous solution containing an oxygen-containing organic accelerator such as formaldehyde and alcohol with ultraviolet light to generate hydrogen. It is characterized by generating.
【００１０】［化学式２］ Ｃｓ（ａ）／Ｋ４Ｎｂ６Ｏ１７ （前記化学式２で，ａはＫ４Ｎｂ６Ｏ１７担体に対する
Ｃｓの支持量を示す重量百分率で，０．０５〜５．０の
値を有する。）[Chemical formula 2] Cs (a) / K4Nb6O17 (In the above chemical formula 2, a is K4Nb6O17Against the carrier
The weight percentage indicating the amount of Cs supported is 0.05 to 5.0.
Has a value. )
【００１１】この技術は環境に無害であり，常温で水素
を発生させ得る利点があるが，水素発生促進剤として含
酸素有機物を使用しなければならないという問題があ
る。即ち含酸素有機物を使用すると，反応後には反応物
の再使用が不可能になるという欠点がある。This technique is harmless to the environment and has the advantage that hydrogen can be generated at room temperature, but has the problem that an oxygen-containing organic substance must be used as a hydrogen generation promoter. That is, when an oxygen-containing organic substance is used, there is a disadvantage that the reactant cannot be reused after the reaction.
【００１２】そして，前記韓国特許出願第９５−３０４
１６号の技術は，下記の化学式３で表示される光触媒を
使用し，環境に無害であり，含酸素有機物促進剤を使用
しなくても多量の水素を常温のような低温で効果的に発
生させることを特徴とする。The Korean Patent Application No. 95-304
The technology of No. 16 uses a photocatalyst represented by the following chemical formula 3, is harmless to the environment, and effectively generates a large amount of hydrogen at a low temperature such as room temperature without using an oxygen-containing organic substance accelerator. It is characterized by making it.
【００１３】［化学式３］ Ｃｓ（ａ）Ｈ（ｃ）／Ｓ（ｂ） （前記化学式３で，ａは担体に対するＣｓの支持量を示
す重量百分率で，６．０以下の値を有する。ＨはＮｉ，
Ｃｏ，Ｆｅの中から選択された助触媒で，Ｃｓの支持
後，混合，支持するものであり，ｃは（Ｃｓ＋Ｈ）に対
するＨの重百分率を示すもので，５０．０以下の値を有
する。Ｓは担体で，ＺｎとＳが１：０．１〜２．８のモ
ル比を有する高純度ＺｎＳ系混合物を示し，ｂはＺｎＳ
系混合物中の無機体の重量百分率で，５０以内の値を有
する。）[Chemical Formula 3] Cs (a) H (c) / S (b) (In Chemical Formula 3, a is a weight percentage indicating the amount of Cs supported on a carrier and has a value of 6.0 or less. Is Ni,
A co-catalyst selected from Co and Fe, which is mixed and supported after Cs is supported, and c indicates a weight percentage of H to (Cs + H) and has a value of 50.0 or less. S is a carrier, Zn and S are a high purity ZnS-based mixture having a molar ratio of 1: 0.1 to 2.8, and b is ZnS
It has a value within 50 by the weight percentage of the inorganic substance in the system mixture. )
【００１４】この技術はやはり環境に無害であり，常温
で含酸素有機物促進剤なしに多量の水素を発生するとい
う大きな利点があるが，触媒の寿命ないし安定性に問題
点がある。すなわち，セシウム（Ｃｓ）のようなアルカ
リ金属を光担体に支持させた場合，水素生成量は韓国特
許出願第９５−７７２１号の場合に比べて数倍増加する
反面，触媒的安定性は非常に弱化する欠点がある。Although this technique is also harmless to the environment and has a great advantage of generating a large amount of hydrogen at room temperature without an oxygen-containing organic substance promoter, it has a problem in the life or stability of the catalyst. That is, when an alkali metal such as cesium (Cs) is supported on an optical carrier, the amount of hydrogen generated increases several times as compared with the case of Korean Patent Application No. 95-7721, but the catalytic stability is extremely high. There is a disadvantage of weakening.
【００１５】また，前記韓国特許出願第９６−４４２１
４号の技術は下記の化学式４で表示される光触媒を使用
する。環境に無害であり，可視光線でも光触媒が活性を
呈する。のみならず，光触媒の製造方法が比較的簡単で
あり，また，得られた触媒の安定性が良く，寿命が電子
供与体及び還元剤の存在に依存するものの極めて長く，
水素発生量も先の特許に比べたいへん良好であることを
特徴とする。[0015] In addition, the Korean Patent Application No. 96-4421.
The technique of No. 4 uses a photocatalyst represented by the following chemical formula 4. It is harmless to the environment and the photocatalyst is active even with visible light. In addition, the method for producing the photocatalyst is relatively simple, the stability of the obtained catalyst is good, and the life depends on the presence of the electron donor and the reducing agent.
It is characterized in that the amount of hydrogen generated is much better than that of the previous patent.
【００１６】［化学式４］ Ｐｔ（ａ）／Ｚｎ［Ｍ（ｂ）］Ｓ （前記化学式４で，ａは光触媒中のＰｔの重量百分率を
示し，０．１〜３．５の値を有し，Ｍは助触媒で，Ｃ
ｏ，Ｆｅ，Ｎｉ，Ｐの中から選択された１種の元素であ
り，ｂは助触媒であるＭ成分のモル％を示す。）[Formula 4] Pt (a) / Zn [M (b)] S (wherein a represents the weight percentage of Pt in the photocatalyst and has a value of 0.1 to 3.5. , M are cocatalysts and C
It is one element selected from o, Fe, Ni, and P, and b indicates mol% of the M component as a promoter. )
【００１７】この技術は先の先行技術と同様に，環境に
無害であり，可視光線領域でも光活性を呈し，Ｃｓの代
わりにＰｔでドーピング（Ｄｏｐｉｎｇ）することによ
り触媒の安定性が増大した。しかしながら助触媒の選択
幅が狭く，水素生成量が多少足りないという問題が残っ
た。また，その製造方法において，２回にわたって焼成
しなければならなく，特に，１次焼成後，エッチング処
理してから再び洗浄しなければならない点が工程上の問
題点として指摘されていた。This technology, like the prior art, is harmless to the environment, exhibits photoactivity even in the visible light region, and the stability of the catalyst is increased by doping with Pt instead of Cs. However, there remains a problem that the selection range of the co-catalyst is narrow and the amount of generated hydrogen is somewhat insufficient. Also, in the manufacturing method, it has been pointed out as a problem in the process that the firing must be performed twice, and in particular, after the primary firing, an etching process must be performed and then cleaning is performed again.
【００１８】[0018]
【発明が解決しようとする課題】本発明は，このような
問題点に鑑みてなされたもので，その目的とするところ
は，光フィルタで調整された可視光線領域でだけでな
く，太陽光線領域でも光触媒が活性を示し，水素生成量
が格段に増加し，寿命も半永久的な水素発生用光触媒を
提供することである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object not only the visible light region adjusted by the optical filter but also the solar light region. However, the purpose is to provide a photocatalyst for hydrogen generation, in which the photocatalyst exhibits activity, the amount of hydrogen generation is remarkably increased, and the lifetime is semi-permanent.
【００１９】[0019]
【課題を解決するための手段】前述した課題を達成する
ために本発明は，下記の化学式１を有することを特徴と
する水素発生用硫化カドミウム（ＣｄＳ）系光触媒であ
る。 ［化学式１］ ｍ（Ａ）／Ｃｄ［Ｍ（Ｂ）］Ｓ （前記式で，ｍは電子受容体で，ドーピングされた金属
を示し，Ｐｔ，Ｒｕ，Ｉｒ，Ｃｏ，Ｒｈ，Ｃｕ，Ｐｄ，
Ｎｉ又はこれらの酸化物による群の中から選択された少
なくとも１種であり，Ａはｍの重量百分率を示すもの
で，０．１０〜２．５０の値を有する。ＭはＶ，Ｃｒ，
Ａｌ，Ｐの中から選択された金属であり，ＢはＭ／（Ｍ
＋Ｃｄ）のモル％を示すもので，０．０５〜２０．００
の値を有する。According to the present invention, there is provided a cadmium sulfide (CdS) -based photocatalyst for generating hydrogen, which has the following chemical formula (1). [Chemical Formula 1] m (A) / Cd [M (B)] S (where m is an electron acceptor and represents a doped metal, and Pt, Ru, Ir, Co, Rh, Cu, Pd,
At least one selected from the group consisting of Ni and their oxides, wherein A indicates the weight percentage of m and has a value of 0.10 to 2.50. M is V, Cr,
Al is a metal selected from P and B is M / (M
+ Cd) in the range of 0.05 to 20.00
Has the value of
【００２０】また，本発明は，Ｍのモル％が０．０５〜
２０．００となるように，Ｃｄ及びＭ含有化合物を水に
溶解した後，これに，反応物としてＨ２Ｓ又はＮａ２Ｓ
を加え，掻き混ぜてＣｄ［Ｍ］Ｓ沈殿物を得，ｐＨが７
を維持するまで，この沈殿物を水で洗浄した後，洗浄さ
れた沈殿物を窒素（気流）雰囲気で真空乾燥させ，この
乾燥されたＣｄ［Ｍ］Ｓ沈殿物に，液状のｍ含有化合物
を，ｍの含有量が０．１０〜２．５０重量％となるよう
に加えてドーピング処理することを特徴とする光触媒の
製造方法である。Further, the present invention relates to the present invention, wherein the molar percentage of M is 0.05 to
So that 20.00, after the Cd and M-containing compounds are dissolved in water, to which, H 2 S or Na 2 S as a reactant
And stirred to obtain a Cd [M] S precipitate.
The precipitate is washed with water until is maintained, and then the washed precipitate is dried under vacuum in a nitrogen (air current) atmosphere. The m-containing compound in liquid form is added to the dried Cd [M] S precipitate. , M in a content of 0.10 to 2.50% by weight and a doping treatment.
【００２１】さらに，本発明は，本発明者の先行技術と
同様に，本発明による光触媒を，電子供与体としてＮａ
２Ｓを，還元剤としてＮａＨ２ＰＯ２をそれぞれ加えた
水に懸濁させ，光フィルタで調整された可視光線領域の
光又は太陽光を照射させることを特徴とする水素製造方
法である。Furthermore, the present invention provides a photocatalyst according to the present invention, as in the prior art of the present inventor, using Na as an electron donor.
A hydrogen production method comprising suspending 2 S in water to which NaH 2 PO 2 is added as a reducing agent, and irradiating light or sunlight in a visible light region adjusted by an optical filter.
【００２２】[0022]
【発明の実施の形態】以下，本発明の実施の形態を詳細
に説明する。前記化学式１において，ｍは電子受容体
（Ｅｌｅｃｔｒｏｎ Ａｃｃｅｐｔｏｒ）で，ドーピン
グ金属を示すものであり，Ｐｔ，Ｒｕ，Ｉｒ，Ｃｏ，Ｒ
ｈ，Ｃｕ，Ｐｄ，Ｎｉの中から選択された金属又はこれ
らの酸化物であり，０．１０〜２．５０重量％の値を有
する。０．１０未満の場合，水素発生量が低下し，触媒
の安定性が悪くなるという問題があり，反面，２．５０
を超える場合，水素発生量が却って減少するのみなら
ず，触媒の製造原価が増加するという問題を生じる。Embodiments of the present invention will be described below in detail. In the above formula 1, m is an electron acceptor, which represents a doping metal, and is composed of Pt, Ru, Ir, Co, R
h, a metal selected from Cu, Pd, and Ni or oxides thereof, having a value of 0.10 to 2.50% by weight. If it is less than 0.10, there is a problem that the amount of generated hydrogen decreases and the stability of the catalyst deteriorates.
When the pressure exceeds 1, not only does the amount of hydrogen generated decrease but also the production cost of the catalyst increases.
【００２３】触媒に添加される成分ＭはＶ，Ｃｒ，Ａ
ｌ，Ｐの中から選択された元素であり，ＢはＭ＋Ｃｄの
Ｍ量をモル％で示したもので，０．０５〜２０．００の
値を有する。この範囲未満の場合には触媒の機能が喪失
されるという問題があり，この範囲を超える場合には水
素生成量が減少するという問題を生じる。The components M added to the catalyst are V, Cr, A
B is an element selected from l and P, and B represents the amount of M of C + Cd in mol% and has a value of 0.05 to 20.00. If it is less than this range, there is a problem that the function of the catalyst is lost, and if it exceeds this range, there is a problem that the amount of generated hydrogen decreases.
【００２４】ＣｄとＳの適切なモル比は１：（０．１〜
２．８）であり，より好ましくは１：（０．６〜１．
４）である。効果的な触媒の能力はこの範囲内で発揮さ
れる。A suitable molar ratio of Cd to S is 1: (0.1 to 0.1
2.8), and more preferably 1: (0.6 to 1.
4). Effective catalyst performance is achieved within this range.
【００２５】光触媒の製造方法において，ｍがＰｔであ
る場合には，窒素雰囲気下で紫外光を照射した後，焼成
してＣｄ［Ｍ］Ｓ上にＰｔがドーピングされるように処
理することが好ましい。好ましい例としては，得られた
Ｃｄ［Ｍ］Ｓ沈殿物にＨｙｄｒｏｇｅｎ Ｈｅｘａｃｈ
ｌｏｒｏｐｌａｔｉｎａｔｅ（Ｈ２ＰｔＣｌ６）を加
え，窒素気流で雰囲気を取り替えた後，紫外光線を照射
し，ｍ（Ｐｔ）の含有量が０．１０〜２．５０となるよ
うにした後，これを，ｐＨが７となるまで水で洗浄し，
１０５〜１２０℃で１．５〜２．５時間真空乾燥させた
後，３００〜４００℃で１．０〜２．０時間酸化焼成
し，３００〜４００℃で１．０〜２．０還元焼成させる
方法が挙げられる。In the method for producing a photocatalyst, when m is Pt, irradiation with ultraviolet light in a nitrogen atmosphere is performed, followed by baking to perform treatment so that Pt is doped on Cd [M] S. preferable. As a preferred example, Hydrogen Hexach is added to the obtained Cd [M] S precipitate.
After adding loroplatinate (H 2 PtCl 6 ) and replacing the atmosphere with a nitrogen stream, irradiating with ultraviolet rays to adjust the content of m (Pt) to 0.10 to 2.50, Wash with water until the pH is 7,
After vacuum drying at 105-120 ° C for 1.5-2.5 hours, oxidizing and firing at 300-400 ° C for 1.0-2.0 hours, and reducing firing at 300-400 ° C for 1.0-2.0 hours. There is a method to make it.
【００２６】また，ｍがＰｔでない場合の好ましい製造
例としては，得られたＣｄ［Ｍ］Ｓ沈殿物にＰｔでない
ｍを含有した化合物を選択し，このｍの含有量が０．１
０〜２．５０の値となるように加えた後，よく掻き混ぜ
ながら濃い塩酸５〜６滴を徐々に入れ，得られたスラリ
ーを超音波で１．０〜５．０分間処理し，１０５〜１２
０℃で１．５〜３．０時間真空乾燥させた後，３００〜
４００℃で１．０〜３．０時間酸化焼成し，３００〜４
００℃で１．０〜３．０時間還元焼成させる方法が挙げ
られる。As a preferable production example when m is not Pt, a compound containing m which is not Pt in the obtained Cd [M] S precipitate is selected, and the content of m is 0.1
After adding the mixture to a value of 0 to 2.50, slowly add 5 to 6 drops of concentrated hydrochloric acid while stirring well, and treat the resulting slurry with ultrasonic waves for 1.0 to 5.0 minutes. ~ 12
After vacuum drying at 0 ° C. for 1.5 to 3.0 hours,
Oxidation and firing at 400 ° C for 1.0 to 3.0 hours, 300 to 4 hours
A method of reducing and firing at 00 ° C. for 1.0 to 3.0 hours is exemplified.
【００２７】Ｐｔでドーピングされた光触媒の製造にお
いて，ｐＨを７に調節した後，乾燥し，酸化及び還元雰
囲気で焼成する理由は，沈殿により得られた光触媒で，
電子受容体であるＰｔを純粋な状態に維持するためであ
る。周知のように，Ｈ２ＰｔＣｌ６の形態で触媒の製造
に導入されたＰｔは，紫外光に露出されることにより硫
化カドミウム（ＣｄＳ）の表面を活性化させるととも
に，遊離されたＳと結合してＰｔＳに変化し，これを３
００〜４００℃の温度で酸化と還元雰囲気で一定時間を
焼成すると，Ｗｕｒｚｉｔｅ構造に変換される。これを
３００〜４００℃の温度で１．０〜２．０時間焼成する
ことにより，電子受容体であるＰｔを純粋な状態のＰｔ
（Ｏ）に転換させることができる。より好ましい焼成温
度は３２０〜３８０℃であるが，この範囲を外れる場
合，触媒の寿命と活性が減少する問題を生じる。In the production of the photocatalyst doped with Pt, the reason for adjusting the pH to 7, drying, and calcination in an oxidizing and reducing atmosphere is that the photocatalyst obtained by precipitation is:
This is for maintaining Pt as an electron acceptor in a pure state. As is well known, Pt introduced into the preparation of the catalyst in the form of H 2 PtCl 6 activates the surface of cadmium sulfide (CdS) by exposure to ultraviolet light and binds to the released S. To PtS, which is 3
When it is fired at a temperature of 00 to 400 ° C. in an oxidizing and reducing atmosphere for a certain time, it is converted into a Wurzite structure. This is fired at a temperature of 300 to 400 ° C. for 1.0 to 2.0 hours to convert Pt as an electron acceptor into pure Pt.
(O). A more preferable calcination temperature is from 320 to 380 ° C, but if the calcination temperature is out of this range, there is a problem that the life and activity of the catalyst are reduced.
【００２８】Ｃｄを含有した化合物の例としてはＣｄＳ
Ｏ４・Ｈ２Ｏ及びＣｄ（ＮＯ３）２・４Ｈ２Ｏなどが挙
げられ，Ｍを含有した化合物の例としてはＶＣｌ３，Ｖ
ＯＳＯ４，ＶＯＣｌ３，Ｋ２Ｃｒ２Ｏ７，Ｃｒ（Ｎ
Ｏ３）３，Ａｌ（ＮＯ３）３，ＡｌＣｌ３，Ｈ３ＰＯ２
などが挙げられる。ｍを含有した化合物の例としてはＲ
ｕＣｌ３，Ｃｏ（ＮＯ３）２，ＣｏＣｌ２，Ｃｏ（ＣＨ
３ＣＯＯ）２，Ｒｈ（ＮＯ ３）３，ＩｒＣｌ３，Ｎｉ
（ＮＯ３）２，ＮｉＣｌ２，Ｐｄ（ＮＯ３）２，ＣｕＣ
ｌ２，Ｃｕ（ＮＯ３）２，ＣｕＳＯ４などが挙げられ
る。Examples of compounds containing Cd include CdS
O4・ H2O and Cd (NO3)2・ 4H2O and others
VCl is an example of a compound containing M3, V
OSO4, VOCl3, K2Cr2O7, Cr (N
O3)3, Al (NO3)3, AlCl3, H3PO2
And the like. Examples of compounds containing m include R
uCl3, Co (NO3)2, CoCl2, Co (CH
3COO)2, Rh (NO 3)3, IrCl3, Ni
(NO3)2, NiCl2, Pd (NO3)2, CuC
l2, Cu (NO3)2, CuSO4Etc.
You.
【００２９】先行技術である本発明者による韓国特許出
願第９６−４４２１４号では，１次焼成後，酸でエッチ
ング処理を行ったが，本発明による一実施の形態では，
光触媒として生成された沈殿物を窒素気流で真空乾燥す
ることにより，１次焼成工程と，これによる酸エッチン
グ処理工程を省略することができる。In Korean Patent Application No. 96-44214 by the present inventor, which is prior art, etching treatment is performed with an acid after primary baking. In one embodiment according to the present invention,
By vacuum drying the precipitate generated as a photocatalyst in a nitrogen stream, the primary firing step and the acid etching step due to this step can be omitted.
【００３０】本発明による一実施の形態における水素製
造方法では，これら光触媒を，電子供与体としてＮａ２
Ｓを０．１５〜０．４０モル，還元剤としてＮａＨ２Ｐ
Ｏ２を０．２０〜０．５０モル加えた１次ないし２次蒸
留水又は単に前処理した水と接触させて懸濁させ，攪拌
しながら５〜８５℃の温度，０．１〜５気圧の条件で光
フィルタで調整された可視光線領域の光及び太陽光を照
射させることで，光反応を起こさせて，水から水素を良
好な効率で発生させることができる。In the hydrogen production method according to one embodiment of the present invention, these photocatalysts are used as electron donors of Na 2
0.15 to 0.40 mol of S, NaH 2 P as a reducing agent
It O 2 primary no added 0.20 to 0.50 mol suspended in contact with the secondary distilled water or simply pre-treated water, stirring temperature of 5 to 85 ° C., 0.1 to 5 atm By irradiating light and sunlight in the visible light region adjusted by the optical filter under the conditions described above, a photoreaction can be caused, and hydrogen can be generated from water with good efficiency.
【００３１】ここで，電子供与体と還元剤の濃度範囲を
維持することが重要であるが，前記範囲未満であると水
素生成量が低下し，また，前記範囲を超えても水素発生
量は増加しない。反応条件は１０〜６０℃の温度と真空
〜２気圧が適当である。Here, it is important to maintain the concentration range of the electron donor and the reducing agent. However, if the concentration is less than the above range, the amount of hydrogen generated is reduced. Does not increase. The reaction conditions are suitably a temperature of 10 to 60 ° C. and a vacuum of 2 atm.
【００３２】本発明の一実施の形態による光触媒は，電
子供与体及び還元剤を反応界に繰り返し投入し反応を進
行させると，寿命が半永久的である。従来のＺｎＳ系光
触媒は，１回の投入で，反応時間が６〜８時間にすぎな
いが，本発明の一実施の形態による光触媒は反応時間が
２０〜２５時間である。これは，触媒活性が持続的に維
持されることを意味する。The photocatalyst according to one embodiment of the present invention has a semi-permanent life when an electron donor and a reducing agent are repeatedly introduced into a reaction field and the reaction proceeds. A conventional ZnS-based photocatalyst has a reaction time of only 6 to 8 hours in one charge, but a photocatalyst according to an embodiment of the present invention has a reaction time of 20 to 25 hours. This means that the catalytic activity is maintained continuously.
【００３３】本発明の実施例はつぎのようである。 ＜製造実施例１及び２＞下記の表１のような組成を有す
るように，水２５０mlにＣｄＳＯ４・ＣｄＳＯ ４・Ｈ２
Ｏと，助触媒としてＫ２Ｃｒ２Ｏ７と，反応物としてＨ
２Ｓをよく掻き混ぜながら加えてＣｄＭＳ沈殿物を得
た。この沈殿物を，ｐＨが７となるまで，水でよく洗浄
した後，１１０℃及び窒素気流の雰囲気で２時間真空乾
燥してＣｄＰＳ粉末を得た。An embodiment of the present invention is as follows. <Production Examples 1 and 2> Having compositions as shown in Table 1 below.
CdSO in 250 ml of water4・ CdSO 4・ H2
O and K as co-catalyst2Cr2O7And H as a reactant
2Add S while stirring well to obtain CdMS precipitate
Was. Wash the precipitate well with water until the pH is 7.
After that, vacuum drying for 2 hours at 110 ° C and nitrogen atmosphere
After drying, a CdPS powder was obtained.
【００３４】この乾燥されたＣｄＰＳ粉末にＲｕＣｌ３
・３Ｈ２ＯをＲｕの含有量が１重量％となるように加え
た後，よく掻き混ぜながら濃い塩酸５〜６滴を徐々に注
入し，得られたスラリーを超音波で３分間処理した。１
１０℃で２時間乾燥した後，３５０℃で１．５時間酸化
雰囲気で焼成して，光触媒ＲｕＯ２（１．０）／Ｃｄ
［Ｃｒ（０．１，４．７６）］を得た。RuCl 3 was added to the dried CdPS powder.
3H 2 O was added so that the Ru content was 1% by weight, and 5 to 6 drops of concentrated hydrochloric acid was gradually injected with good stirring, and the resulting slurry was treated with ultrasonic waves for 3 minutes. 1
After drying at 10 ° C. for 2 hours, baking in an oxidizing atmosphere at 350 ° C. for 1.5 hours, the photocatalyst RuO 2 (1.0) / Cd
[Cr (0.1, 4.76)] was obtained.
【００３５】＜製造実施例３及び４＞製造実施例１にお
いて，助触媒としてＫ２Ｃｒ２Ｏ７の代わりにＡｌ（Ｎ
Ｏ３）３を使用して，光触媒ＲｕＯ２（１．０）／Ｃｄ
［Ａｌ（０．５，４．７６）］Ｓを得た。<Production Examples 3 and 4> In Production Example 1, Al (N) was used instead of K 2 Cr 2 O 7 as a promoter.
Photocatalyst RuO 2 (1.0) / Cd using O 3 ) 3
[Al (0.5,4.76)] S was obtained.
【００３６】＜製造実施例５＞製造実施例１において，
助触媒としてＫ２Ｃｒ２Ｏ７の代わりにＨ３ＰＯ２を使
用して，光触媒ＲｕＯ２（１．０）／Ｃｄ［Ｐ（４．７
６）］Ｓを得た。<Production Example 5> In Production Example 1,
Using H 3 PO 2 instead of K 2 Cr 2 O 7 as a promoter, a photocatalyst RuO 2 (1.0) / Cd [P (4.7
6)] S was obtained.
【００３７】＜製造実施例６＞製造実施例５において，
酸化雰囲気で焼成した後，再び３５０℃で１.５時間還
元雰囲気で焼成し，ＲｕＣｌ３・３Ｈ２ＯをＲｕの含有
量が１重量％となるように加えて，光触媒Ｒｕ（１．
０）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Manufacturing Example 6> In Manufacturing Example 5,
After baking in an oxidizing atmosphere, baking is again performed at 350 ° C. for 1.5 hours in a reducing atmosphere, and RuCl 3 .3H 2 O is added so that the Ru content becomes 1% by weight, and the photocatalyst Ru (1.
0) / Cd [P (4.76)] S was obtained.
【００３８】＜製造実施例７＞製造実施例６において，
ＲｕＣｌ３・３Ｈ２Ｏの代わりにＮｉＣｌ２・６Ｈ２Ｏ
をＮｉの含有量が１重量％となるように加て，光触媒Ｎ
ｉ（１．０）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Production Example 7> In Production Example 6,
NiCl 2 · 6H 2 O in place of RuCl 3 · 3H 2 O
Is added so that the Ni content is 1% by weight, and the photocatalyst N
i (1.0) / Cd [P (4.76)] S was obtained.
【００３９】＜製造実施例８＞製造実施例６において，
助触媒としてＨ３ＰＯ２の代わりにＶＣｌ３を使用し
て，光触媒Ｎｉ（１．０）／Ｃｄ［Ｖ（４．７６）］Ｓ
を得た。<Eighth Embodiment> In the sixth embodiment,
Using VCl 3 instead of H 3 PO 2 as a promoter, the photocatalyst Ni (1.0) / Cd [V (4.76)] S
I got
【００４０】＜製造実施例９及び１０＞製造実施例７に
おいて，Ｎｉの含有量がそれぞれ０．５，２．０重量％
となるようにして，光触媒Ｎｉ（０．５，２．０）／Ｃ
ｄ［Ｐ（４．７６）］Ｓを得た。<Production Examples 9 and 10> In Production Example 7, the content of Ni was 0.5 and 2.0% by weight, respectively.
And the photocatalyst Ni (0.5, 2.0) / C
d [P (4.76)] S was obtained.
【００４１】＜製造実施例１１＞製造実施例７におい
て，還元雰囲気での焼成段階を省略して，光触媒ＮｉＯ
（１．０）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Production Example 11> In Production Example 7, the photocatalyst NiO
(1.0) / Cd [P (4.76)] S was obtained.
【００４２】＜製造実施例１２＞製造実施例７におい
て，ＮｉＣｌ２・６Ｈ２Ｏの代わりにＰｄ（ＮＯ３）２
を使用して，光触媒Ｐｄ（１．０）／Ｃｄ［Ｐ（４．７
６）］Ｓを得た。<Production Example 12> In Production Example 7, Pd (NO 3 ) 2 was used instead of NiCl 2 .6H 2 O.
Using the photocatalyst Pd (1.0) / Cd [P (4.7
6)] S was obtained.
【００４３】＜製造実施例１３＞製造実施例１２におい
て，還元雰囲気での焼成段階を省略して，光触媒ＰｄＯ
（１．０）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Production Example 13> In Production Example 12, the sintering step in a reducing atmosphere was omitted, and the photocatalyst PdO
(1.0) / Cd [P (4.76)] S was obtained.
【００４４】＜製造実施例１４＞製造実施例１２におい
て，Ｐｄ（ＮＯ３）２の代わりにＲｈ（ＮＯ３）３を使
用して，光触媒Ｒｈ（１．０）／Ｃｄ［Ｐ（４．７
６）］Ｓを得た。<Production Example 14> In Production Example 12, the photocatalyst Rh (1.0) / Cd [P (4.7) was obtained by using Rh (NO 3 ) 3 instead of Pd (NO 3 ) 2.
6)] S was obtained.
【００４５】＜製造実施例１５＞製造実施例１２におい
て，Ｐｄ（ＮＯ３）２の代わりにＣｏ（ＮＯ３）２を使
用して，光触媒Ｃｏ（１．０）／Ｃｄ［Ｐ（４．７
６）］Ｓを得た。<Production Example 15> In Production Example 12, Co (NO 3 ) 2 was used in place of Pd (NO 3 ) 2 to produce a photocatalyst Co (1.0) / Cd [P (4.7).
6)] S was obtained.
【００４６】＜製造実施例１６＞製造実施例１２におい
て，Ｐｄ（ＮＯ３）２の代わりにＩｒＣｌ３を使用し
て，光触媒Ｉｒ（１．０）／Ｃｄ［Ｐ（４．７６）］Ｓ
を得た。<Production Example 16> In Production Example 12, the photocatalyst Ir (1.0) / Cd [P (4.76)] S was prepared by using IrCl 3 instead of Pd (NO 3 ) 2 .
I got
【００４７】＜製造実施例１７＞製造実施例１６と同様
に実施して得た乾燥粉末Ｃｄ［Ｐ（４．７６）］ＳにＨ
２ＰｔＣｌ６をＰｔ含有量が０．８重量％となるように
加えた後，窒素雰囲気で０．５時間４５０Ｗの高圧水銀
灯を使用して４ｃｍの距離で紫外光を照射した。水でｐ
Ｈが７となるまで洗浄した後，１１０℃で２時間乾燥
し，３５０℃で１．５時間酸化雰囲気で焼成し，これを
再び３５０℃で１．５時間還元雰囲気で焼成して光触媒
Ｐｔ（０．８）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Manufacturing Example 17> Same as Manufacturing Example 16
To dry powder Cd [P (4.76)] S obtained by
2PtCl6So that the Pt content is 0.8% by weight.
After adding, high pressure mercury of 450W for 0.5 hour in nitrogen atmosphere
Ultraviolet light was applied at a distance of 4 cm using a lamp. P with water
After washing until H becomes 7, dry at 110 ° C for 2 hours
And calcined in an oxidizing atmosphere at 350 ° C. for 1.5 hours.
Photocatalyst fired again at 350 ° C for 1.5 hours in reducing atmosphere
Pt (0.8) / Cd [P (4.76)] S was obtained.
【００４８】＜製造実施例１８＞製造実施例１７におい
て，Ｐｔの含有量が０．４重量％となるようにして光触
媒Ｐｔ（０．４）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Production Example 18> In Production Example 17, the photocatalyst Pt (0.4) / Cd [P (4.76)] S was obtained so that the Pt content was 0.4% by weight. Was.
【００４９】＜製造実施例１９＞製造実施例１７におい
て，Ｐｔの含有量が２．０重量％となるようにして光触
媒Ｐｔ（２．０）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Production Example 19> In Production Example 17, the photocatalyst Pt (2.0) / Cd [P (4.76)] S was obtained so that the Pt content was 2.0% by weight. Was.
【００５０】＜製造実施例２０＞製造実施例１６と同様
に実施して得た乾燥粉末Ｃｄ［Ｐ（４．７６）］ＳにＨ
２ＰｔＣｌ６をＰｔ含有量が０．８重量％となるように
加えた後，窒素雰囲気で０．５時間４５０Ｗの高圧水銀
灯を使用して４ｃｍの距離で紫外光を照射した。水でｐ
Ｈが７となるまで洗浄した後，１１０℃で２時間乾燥
し，この乾燥されたＰｔ／ＣｄＰＳ粉末にＲｕの含有量
が１．０重量％となるようにＲｕＣｌ３・３Ｈ２Ｏを加
えた後，よく掻き混ぜながら濃い塩酸を５〜６滴徐々に
注入した。得られたスラリーを超音波で３分間処理し，
１１０℃で２時間乾燥した後，３５０℃で１．５時間還
元雰囲気で焼成して光触媒Ｐｔ（０．８）／Ｃｄ［Ｐ
（４．７６）］Ｓ／ＲｕＯ２（１．０）を得た。<Production Example 20> Same as Production Example 16
To dry powder Cd [P (4.76)] S obtained by
2PtCl6So that the Pt content is 0.8% by weight.
After adding, high pressure mercury of 450W for 0.5 hour in nitrogen atmosphere
Ultraviolet light was applied at a distance of 4 cm using a lamp. P with water
After washing until H becomes 7, dry at 110 ° C for 2 hours
And the Ru content of the dried Pt / CdPS powder.
Is adjusted to be 1.0% by weight.3・ 3H2Add O
And slowly add 5-6 drops of concentrated hydrochloric acid while stirring well.
Injected. The resulting slurry is treated with ultrasound for 3 minutes,
After drying at 110 ° C for 2 hours, returning at 350 ° C for 1.5 hours
Calcined in the original atmosphere and photocatalyst Pt (0.8) / Cd [P
(4.76)] S / RuO2(1.0) was obtained.
【００５１】＜製造実施例２１＞製造実施例２０におい
て，ＲｕＣｌ３・３Ｈ２Ｏの代わりにＮｉＣｌ２・６Ｈ
２Ｏを加えて，光触媒Ｐｔ（０．８）／Ｃｄ［Ｐ（４．
７６）］Ｓ／ＮｉＯ（１．０）を得た。 ＜製造実施例２２＞<Production Example 21> In Production Example 20,
And RuCl3・ 3H2NiCl instead of O2・ 6H
2O, and the photocatalyst Pt (0.8) / Cd [P (4.
76)] S / NiO (1.0) was obtained. <Production Example 22>
【００５２】製造実施例１７において，Ｐｔの含有量が
０．８重量％となるようにして光触媒Ｐｔ（０．８）／
Ｃｄ［Ｐ（４．７６）］Ｓを得た。In Production Example 17, the photocatalyst Pt (0.8) / photocatalyst was adjusted so that the Pt content was 0.8% by weight.
Cd [P (4.76)] S was obtained.
【００５３】＜製造実施例２３＞製造実施例７におい
て，ＮｉＣｌ２・６Ｈ２Ｏの代わりにＣｕ（ＮＯ３）２
を使用して光触媒Ｃｕ（１．０）／Ｃｄ［Ｐ（４．７
６）］Ｓを得た。<Production Example 23> In Production Example 7, Cu (NO 3 ) 2 was used instead of NiCl 2 .6H 2 O.
Using a photocatalyst Cu (1.0) / Cd [P (4.7
6)] S was obtained.
【００５４】＜製造実施例２４＞製造実施例１におい
て，Ｃｒの含有量が２５重量％となるように変更して光
触媒ＲｕＯ２（１．０）／Ｃｄ［Ｃｒ（２５）］Ｓを得
た。<Production Example 24> The photocatalyst RuO 2 (1.0) / Cd [Cr (25)] S was obtained in the same manner as in Production Example 1 except that the Cr content was changed to 25% by weight. .
【００５５】＜製造実施例２５＞製造実施例７におい
て，Ｎｉの含有量が３重量％となるように変更して光触
媒Ｎｉ（３．０）／Ｃｄ［Ｐ（４．７６）］Ｓを得た。<Production Example 25> In Production Example 7, the photocatalyst Ni (3.0) / Cd [P (4.76)] S was obtained by changing the Ni content to 3% by weight. Was.
【００５６】＜実施例１〜２３及び比較例１及び２＞製
造実施例１〜２５で得られた光触媒０．５ｇをＮａ２Ｓ
濃度が０．２４モル，ＮａＨ２ＰＯ２濃度が０．３５モ
ルである水溶液５００mlに入れて懸濁し，閉鎖気体循環
界光反応装置に入れ３００rpmで攪拌しながら，常温，
常圧で５００ＷのＸｅランプと紫外光を遮断する光フィ
ルタを使用して４ｃｍの距離で可視光を照射した。発生
した水素量をガスクロマトグラフィー（Ｇａｓ Ｃｈｒ
ｏｍａｔｏｇｒａｐｈｙ）及びビュレット（Ｂｕｒｅｔ
ｔｅ）で定量分析した。その結果を下記の表１にしめ
す。[0056] The photocatalyst 0.5g obtained in <Examples 1 to 23 and Comparative Examples 1 and 2> Preparation Example 1 to 25 Na 2 S
The suspension was placed in 500 ml of an aqueous solution having a concentration of 0.24 mol and a NaH 2 PO 2 concentration of 0.35 mol. The suspension was placed in a closed gas circulation field light reactor and stirred at 300 rpm at room temperature.
Visible light was irradiated at a distance of 4 cm using a 500 W Xe lamp at normal pressure and an optical filter that blocks ultraviolet light. The amount of generated hydrogen was determined by gas chromatography (Gas Chr).
Omatography and Buret
te) was quantitatively analyzed. The results are shown in Table 1 below.
【００５７】＜実施例２４＞本実施例は本発明の一実施
の形態による光触媒の寿命を確認するためのものであ
る。製造実施例１７により得られた光触媒０．５ｇをＮ
ａ２Ｓ濃度が０．２４モル，ＮａＨ２ＰＯ２濃度が０．
３５モルである水溶液５００mlに入れ，総１００時間に
わたって，２０時間ごとに，Ｎａ２Ｓ０．２４モルおよ
びＮａＨ２ＰＯ ２０．３５モルを，繰り返して投入して
発生した水素量を測定した。その結果，発生気体量は平
均４０２（ｍｌ／ｈｒ）で，実施例１７で得られた水素
発生量４２２（ｍｌ／ｈｒ）と類似した。これは，光触
媒の寿命が半永久的であることを意味する。<Embodiment 24> This embodiment is an embodiment of the present invention.
To confirm the life of the photocatalyst
You. 0.5 g of the photocatalyst obtained in Production Example 17 was
a2S concentration 0.24 mol, NaH2PO2The concentration is 0.
In 500 ml of 35 mol aqueous solution, 100 hours total
For every 20 hours, Na20.24 mol of S
And NaH2PO 20.35 mol was repeatedly charged
The amount of generated hydrogen was measured. As a result, the amount of generated gas is flat.
Hydrogen obtained in Example 17 at an average of 402 (ml / hr)
It was similar to the generated amount 422 (ml / hr). This is
It means that the life of the medium is semi-permanent.
【００５８】[0058]
【表１】 [Table 1]
【００５９】以上，添付図面を参照しながら本発明にか
かる硫化カドミウム系水素発生用光触媒及びその製造方
法とそれを用いる水素の製造方法の好適な実施形態につ
いて説明したが，本発明はかかる例に限定されない。当
業者であれば，特許請求の範囲に記載された技術的思想
の範疇内において各種の変更例または修正例に想到し得
ることは明らかでありそれについても当然に本発明の技
術的範囲に属するものと了解される。The preferred embodiments of the cadmium sulfide-based hydrogen generating photocatalyst, the method for producing the same, and the method for producing hydrogen using the same according to the present invention have been described above with reference to the accompanying drawings. Not limited. It is obvious that those skilled in the art can conceive various changes or modifications within the scope of the technical idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood.
【００６０】[0060]
【発明の効果】以上，詳細に説明したように本発明によ
れば，光フィルタで調整された可視光線領域でだけでな
く，太陽光線領域でも光触媒が活性を示し，水素生成量
が格段に増加し，寿命も半永久的な水素発生用光触媒を
提供することである。As described above in detail, according to the present invention, the photocatalyst is active not only in the visible light region adjusted by the optical filter but also in the sunlight region, and the amount of hydrogen generation is remarkably increased. Another object of the present invention is to provide a photocatalyst for hydrogen generation having a semi-permanent life.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 37/03 Ｂ０１Ｊ 37/03 Ｚ 37/34 37/34 Ｃ０１Ｂ 3/04 Ｃ０１Ｂ 3/04 Ａ (72)発明者 白 振旭 大韓民国大田廣域市儒城区道龍洞431番地 ７棟205号 Ｆターム(参考） 4G069 AA02 AA03 AA08 AA09 BA46A BB05C BB08C BB09A BB09B BB10C BB12C BC02C BC03C BC16A BC16B BC31A BC31B BC36A BC36B BC54A BC54B BC58A BC67A BC67B BC68A BC68B BC70A BC70B BC71A BC71B BC72A BC72B BC74A BC74B BC75A BC75B BD07A BD07B BD08A BD08B CC33 FB08 FB30 FB57 FC06 FC07 FC08 FC09 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 37/03 B01J 37/03 Z 37/34 37/34 C01B 3/04 C01B 3/04 A (72) Inventor Hakushin Asahi F-term (reference) 4G069 AA02 AA03 AA08 AA09 BA46A BB05C BB08C BB09A BB09B BB10C BB12C BC02C BC03C BC16A BCBC BCA BCB BCB BCA BCB BCB BCA BCA BCB BCB BCA BCA BCB BCA BCB BCA BCA BCBC BC BC BC68A BC68B BC70A BC70B BC71A BC71B BC72A BC72B BC74A BC74B BC75A BC75B BD07A BD07B BD08A BD08B CC33 FB08 FB30 FB57 FC06 FC07 FC08 FC09
Claims (14)
る水素発生用硫化カドミウム（ＣｄＳ）系光触媒。 ［化学式１］ ｍ（Ａ）／Ｃｄ［Ｍ（Ｂ）］Ｓ （前記式で，ｍは電子受容体で，ドーピングされた金属
を示し，Ｐｔ，Ｒｕ，Ｉｒ，Ｃｏ，Ｒｈ，Ｃｕ，Ｐｄ，
Ｎｉ又はこれらの酸化物による群の中から選択された少
なくとも１種であり，Ａはｍの重量百分率を示すもの
で，０．１０〜２．５０の値を有する。ＭはＶ，Ｃｒ，
Ａｌ，Ｐの中から選択された金属であり，ＢはＭ／（Ｍ
＋Ｃｄ）のモル％を示すもので，０．０５〜２０．００
の値を有する。）1. A cadmium sulfide (CdS) -based photocatalyst for generating hydrogen, having the following chemical formula 1. [Chemical Formula 1] m (A) / Cd [M (B)] S (where m is an electron acceptor and represents a doped metal, and Pt, Ru, Ir, Co, Rh, Cu, Pd,
At least one selected from the group consisting of Ni and their oxides, wherein A indicates the weight percentage of m and has a value of 0.10 to 2.50. M is V, Cr,
Al is a metal selected from P and B is M / (M
+ Cd) in the range of 0.05 to 20.00
Has the value of )
であることを特徴とする請求項１記載の水素発生用硫化
カドミウム（ＣｄＳ）系光触媒。2. The molar ratio of Cd: S is 1: 0.1 to 2.8.
The cadmium sulfide (CdS) -based photocatalyst for hydrogen generation according to claim 1, wherein
であることを特徴とする請求項１記載の水素発生用硫化
カドミウム（ＣｄＳ）系光触媒。3. The molar ratio of Cd: S is 1: 0.6-1.4.
The cadmium sulfide (CdS) -based photocatalyst for hydrogen generation according to claim 1, wherein
るように，Ｃｄ及び前記Ｍ含有化合物を水に溶解した
後，これに，反応物としてＨ２Ｓ，Ｎａ２Ｓのいずれか
１種を加え，掻き混ぜてＣｄ［Ｍ］Ｓ沈殿物を得，ｐＨ
が７を維持するまで，前記沈殿物を水で洗浄した後，窒
素（気流）雰囲気と１０５〜１２０℃の温度で１．５〜
３．０時間真空乾燥させた後，この乾燥された前記Ｃｄ
［Ｍ］Ｓ沈殿物に，液状の前記ｍ含有化合物を，前記ｍ
の含有量が全光触媒の０．１０〜２．５０重量％となる
ように加えてドーピング処理することを特徴とする硫化
カドミウム（ＣｄＳ）系光触媒の製造方法。4. After dissolving Cd and the M-containing compound in water such that the value of M is 0.05 to 20.00, either of H 2 S or Na 2 S is added as a reactant. Add one or more and stir to obtain Cd [M] S precipitate, pH
The precipitate was washed with water until the temperature of the solution maintained at 7, and then the temperature was increased to 1.5 to 120 ° C. and a temperature of 105 to 120 ° C.
After vacuum drying for 3.0 hours, the dried Cd
[M] Add the liquid m-containing compound to the S
A cadmium sulfide (CdS) -based photocatalyst, characterized in that a doping treatment is carried out in addition to a content of 0.10 to 2.50% by weight of the total photocatalyst.
は焼成工程を含むことを特徴とする請求項４記載の硫化
カドミウム（ＣｄＳ）系光触媒の製造方法。5. The method for producing a cadmium sulfide (CdS) -based photocatalyst according to claim 4, wherein the doping method includes an ultraviolet light irradiation or firing step.
４，ＶＯＣｌ３，Ｋ ２Ｃｒ２Ｏ７，Ｃｒ（ＮＯ３）３，
Ａｌ（ＮＯ３）３，ＡｌＣｌ３，Ｈ３ＰＯ２による群の
中から選択された少なくとも１種であることを特徴とす
る請求項４または５記載の硫化カドミウム（ＣｄＳ）系
光触媒の製造方法。6. The M-containing compound is VCl3, VOSO
4, VOCl3, K 2Cr2O7, Cr (NO3)3,
Al (NO3)3, AlCl3, H3PO2Group of
At least one selected from the group consisting of:
The cadmium sulfide (CdS) system according to claim 4 or 5.
A method for producing a photocatalyst.
ｕＣｌ３，Ｃｏ（ＮＯ３）２，ＣｏＣｌ２，Ｃｏ（ＣＨ
３ＣＯＯ）２，ＲｈＣｌ３，Ｒｈ（ＮＯ３） ３，ＩｒＣ
ｌ３，Ｎｉ（ＮＯ３）２，ＮｉＣｌ２，Ｐｄ（ＮＯ３）
２，ＣｕＣｌ ２，Ｃｕ（ＮＯ３）２，ＣｕＳＯ４による
群の中から選択された少なくとも１種であることを特徴
とする請求項４または５記載の硫化カドミウム（Ｃｄ
Ｓ）系光触媒の製造方法。7. The m-containing compound is H2PtCl6, R
uCl3, Co (NO3)2, CoCl2, Co (CH
3COO)2, RhCl3, Rh (NO3) 3, IrC
l3, Ni (NO3)2, NiCl2, Pd (NO3)
2, CuCl 2, Cu (NO3)2, CuSO4by
Characterized by at least one selected from the group
Cadmium sulfide (Cd) according to claim 4 or 5,
S) A method for producing a photocatalyst.
光を照射してドーピング処理する工程を含むことを特徴
とする請求項４記載の硫化カドミウム（ＣｄＳ）系光触
媒の製造方法。8. The method for producing a cadmium sulfide (CdS) -based photocatalyst according to claim 4, further comprising a step of irradiating ultraviolet light in a nitrogen atmosphere to perform doping when m is Pt.
酸化焼成及び還元焼成を行うことを特徴とする請求項４
記載の硫化カドミウム（ＣｄＳ）系光触媒の製造方法。9. When m is Pt, after irradiation with ultraviolet light,
5. An oxidation firing and a reduction firing are performed.
A method for producing the cadmium sulfide (CdS) -based photocatalyst described above.
ることを特徴とする請求項９記載の硫化カドミウム（Ｃ
ｄＳ）系光触媒の製造方法。10. The cadmium sulfide (C) according to claim 9, wherein the firing temperature is 300 to 400 ° C.
dS) A method for producing a photocatalyst.
及びＣｄ（ＮＯ３） ２・４Ｈ２Ｏを含むことを特徴とす
る請求項４または５記載の硫化カドミウム（ＣｄＳ）系
光触媒の製造方法。11. The Cd-containing material is CdSO4・ H2O
And Cd (NO3) 2・ 4H2Characterized by containing O
The cadmium sulfide (CdS) system according to claim 4 or 5.
A method for producing a photocatalyst.
加える工程を更に含むことを特徴とする請求項４または
５記載の硫化カドミウム（ＣｄＳ）系光触媒の製造方
法。12. The method for producing a cadmium sulfide (CdS) -based photocatalyst according to claim 4, further comprising a step of adding hydrochloric acid before drying when m is not Pt.
としてＮａ２Ｓを０．１５〜０．４０モル，還元剤とし
てＮａＨ２ＰＯ２を０．２０〜０．５０モル加えた水と
接触させて懸濁させ，攪拌しながら，光フィルタ（Ｌｉ
ｇｈｔ Ｆｉｌｔｅｒ）で調整された可視光線領域の光
又は太陽光を照射して反応させることを特徴とする光触
媒を用いる水素発生方法。13. The photocatalyst according to claim 1, comprising 0.15 to 0.40 mol of Na 2 S as an electron donor and 0.20 to 0.50 mol of NaH 2 PO 2 as a reducing agent. Contact and suspend, and with stirring, light filter (Li
A method for generating hydrogen using a photocatalyst, which comprises irradiating light or sunlight in a visible light region adjusted by a G.H.
び真空〜２気圧であることを特徴とする請求項１３記載
の光触媒を用いる水素発生方法。14. The method for generating hydrogen using a photocatalyst according to claim 13, wherein the reaction conditions are a temperature of 10 to 60 ° C. and a vacuum to 2 atm.
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